JP2002105180A - Method for producing hydride of ring-opening polymer - Google Patents

Abstract

(57) Abstract: According to the present invention, there is provided an industrial method for obtaining a hydrogenated cyclic olefin ring-opened polymer having excellent solubility in an organic solvent. A ring-opening metathesis polymerization of cyclic olefins in the presence of a solvent using a ruthenium compound coordinated with a carbene compound containing a hetero atom having at least one secondary or tertiary alkyl group. After doing
Hydrogenate at least 50% of carbon-carbon double bonds in the ring-opened polymer main chain.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a hydrogenated cyclic olefin ring-opened polymer having excellent solubility in a solvent.

[0002]

2. Description of the Related Art Ring-opening polymers of cyclic olefins have been well known and their polymerization (metathesis ring-opening polymerization).
As the catalyst used for the above, compounds containing transition metals of Groups 4 to 6 of the periodic table, such as titanium, zirconium, vanadium, tungsten, molybdenum, and titanium are used. Recently, those containing ruthenium and osmium, which are transition metals of Group VIII of the periodic table, are attracting attention because they are less susceptible to water, alcohol, and the like. Ruthenium-based catalysts composed of these compounds have been improved. ing. Japanese Patent Application Laid-Open No. 9-512828 discloses a ruthenium compound having phosphine as a ligand.
No. 5,182, also reports an example in which a cyclic olefin is polymerized with the ruthenium compound, and then the obtained ring-opened polymer is hydrogenated. However, according to studies by the present inventors, when dicyclopentadienes or tetracyclododecenes are polymerized using the ruthenium compound,
As the polymerization proceeds, the formed polymer is apt to precipitate, and the solubility of the hydrogenated hydride of the ring-opened polymer in the solvent becomes extremely poor, making it difficult to recover the polymer or remove the catalyst.

[0003] International Publications WO 99/51344 and WO 00/15339 disclose ruthenium compounds having a heterocyclic carbene compound having nitrogen as a ligand, and include cyclooctadiene and the like. Only polymerized examples have been reported.

Therefore, the present inventors have made the following general formula (1):
[1,3-bis (2,4,6-trimethylphenyl) imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride represented by

[0005]

Embedded image (In the formula, Mes represents a 2,4,6-trimethylphenyl group, Cy represents a cyclohexyl group, and Ph represents a phenyl group. The same applies to the following general formula (2).)

Alternatively, [1,3] represented by the following general formula (2)
-Bis (2,4,6-trimethylphenyl) imidazolidin-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride

[0007]

Embedded image

[0008] After ring-opening polymerization of dicyclopentadiene using a ruthenium compound having a nitrogen-containing heterocyclic carbene compound as a ligand, the carbon-carbon double bond of the polymer is hydrogenated. The resulting hydride had poor solubility in cyclohexane at room temperature, and had to be heated to 80 ° C. or higher in order to dissolve it at 20% by weight.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a ring-opened polymer hydride of a cyclic olefin having excellent solubility in a solvent.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, the secondary carbon or the tertiary carbon was replaced with a ruthenium compound as described above. By using a ruthenium compound in which a heterocyclic carbene compound having a specific structure bonded to an atom as a ligand, it was found that the solubility of the obtained hydrogenated polymer in a solvent was significantly improved, and the present invention was completed. Was.

Thus, according to the present invention, a compound containing a hetero atom to which a secondary or tertiary carbon is bonded and a methylene free radical is coordinated with a ruthenium atom using a ruthenium compound. A method for obtaining a ring-opened polymer hydride by subjecting a cyclic olefin to ring-opening metathesis polymerization in the presence of a solvent and then hydrogenating at least 50% of carbon-carbon double bonds in the ring-opened polymer main chain. Is done.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a ring-opening metathesis of a cyclic olefin in the presence of a solvent using a ruthenium compound having a specific structure in which a compound containing a hetero atom and a methylene free radical is coordinated to ruthenium. After polymerization, at least 50% of carbon-carbon double bonds in the main chain of the ring-opened polymer are hydrogenated. According to the above method, the hydrogenated ring-opening polymer is obtained as a solution dissolved in an organic solvent.
The ruthenium compound used in the present invention has ruthenium as a central metal, and has a compound containing a hetero atom and a methylene free radical (hereinafter referred to as a carbene compound) as a ligand of the ruthenium. . Further, a secondary carbon or a tertiary carbon is bonded to a hetero atom in the carbene compound, and the carbene compound is coordinated to ruthenium by a methylene free radical. The carbene compound is a generic term for compounds having a methylene free radical, and refers to a compound having an uncharged divalent carbon atom represented by (> C :). The carbene is generally present as an unstable intermediate generated during the reaction, but can be isolated as a relatively stable carbene compound having a hetero atom. In the above, a secondary carbon bonded to a hetero atom refers to a carbon bonded to two carbons other than a hetero atom by a single bond, and a tertiary carbon is also three carbons other than a hetero atom. A substance that is bonded to carbon by a single bond. Therefore, those not considered as tertiary carbons, such as carbons forming an aromatic ring, are not included. Such a ruthenium compound is specifically,
It is represented by the following general formula (3).

[0013]

Embedded image (Wherein X ¹ and X ² independently represent an anionic ligand, L ¹ represents a carbene compound containing a heteroatom to which a secondary or tertiary carbon is bonded,
L ² represents any neutral electron donor. R ¹ and R
² independently represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. )

The above-mentioned hetero atom is an atom belonging to Group 15 and Group 16 of the periodic table, and specifically, a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom ( S), arsenic atoms (As), selenium atoms (Se) and the like. Among them, N, O, P, and S are preferable for obtaining a stable carbene compound, and N and P are particularly preferable. Moreover, carbene compound L ¹ containing a heteroatom, a secondary carbon or tertiary carbon, as long as it is bonded to the hetero atom is not particularly limited, the following general formula heteroatom is N The compound represented by (4) is more preferred.

[0015]

Embedded image Wherein R ³ is N through a secondary or tertiary carbon
Is a hydrocarbon group having 1 to 20 carbon atoms bonded to R
³ may include a halogen atom, O, N, S, P or a silicon atom (Si). R ^{4 to} R ⁶ independently represent a hydrogen atom or a halogen atom, O, N, S, P or Si
A hydrocarbon group having 1 to 20 carbon atoms which may contain
³ may be the same. Further, R ⁵ and R ⁶ may combine with each other to form a ring. )

Among the compounds represented by the general formula (4), a cyclic carbene compound in which R ⁵ and R ⁶ are bonded to each other to form a ring is more preferable because it is stable, and is represented by the following general formula (5). Substituted imidazoline-2-ylidene, and substituted imidazolidin-2 represented by the following general formula (6)
-Ylidene is most preferred.

[0017]

Embedded image

[0018]

Embedded image

(In the formulas 5 and 6, R ⁷ , R ⁸ , R ¹³ and R ¹⁴ are each independently a halogen atom, O, N, S, P
Or a hydrocarbon group having 1 to 20 carbon atoms which may contain Si, and R ^{9 to} R ¹² and R ^{15 to} R ¹⁸ are each independently a hydrogen atom or a halogen atom, O, N, S, P or S
and represents a hydrocarbon group having 1 to 20 carbon atoms which may contain i.
R ⁷ and R ⁸ and R ¹³ and R ¹⁴ may combine with each other to form an aliphatic ring, and R ¹¹ and R ¹² , R ¹⁷ and R
¹⁸ may combine with each other to form a ring. )

Specific examples of the compound represented by the general formula (5) include 1,3-diisopropyl-4-imidazoline-
2-ylidene, 1,3-dicyclohexyl-4-imidazoline-2-ylidene, 1,3-di (1′-phenylethyl) -4-imidazoline-2-ylidene, 1,3-di (diphenylmethyl) -4 -Imidazoline-2-ylidene, 1,3-di (1'-naphthylethyl) -4-imidazoline-2-ylidene, 1,3-diadamantyl-4-
Imidazoline-2-ylidene, 1,3-di (1'-cyclohexylethyl) -4-imidazoline-2-ylidene, 1,3-diisopropyl-4,5-diphenyl-4
-Imidazoline-2-ylidene, 1,3-dicyclohexylbenzimidazoline-2-ylidene, and the like. Specific examples of the compound represented by the general formula (6) include:
1,3-diisopropylimidazolidin-2-ylidene, 1,3-dicyclohexylimidazolidin-2-ylidene, 1,3-di (1′-phenylethyl) imidazolidine-2-ylidene, 1,3-di (diphenyl Methyl) imidazolidine-2-ylidene, 1,3-di (1 ′
-Naphthylethyl) imidazolidine-2-ylidene,
1,3-diadamantyl imidazolidine-2-ylidene, 1,3-di (1′-cyclohexylethyl) imidazolidin-2-ylidene, 1,3-diisopropyl-
4,5-diphenylimidazolidin-2-ylidene,
1,3-dicyclohexyl-hexahydrobenzimidazoline-2-ylidene and the like. In addition to the compounds represented by the general formulas (5) and (6), 3
-(Diphenylmethyl) -2,3,4,5-tetrahydrothiazole-2-ylidene, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N,
N ', N'-tetraisopropylformamidinylidene and the like can be mentioned.

Among the above compounds, those in which a bulky secondary hydrocarbon group or a bulky tertiary hydrocarbon group is bonded to a hetero atom are more preferable. Specifically, 1,3-di (1 '-Phenylethyl) -4-imidazoline-2-ylidene, 1,3-di (diphenylmethyl) -4-imidazoline-2-ylidene, 1,3-di (1'-naphthylethyl) -4-imidazoline-2 -Ilidene, 1,3-di (1'-cyclohexylethyl) -4-imidazoline-
2-ylidene, 1,3-di (1′-phenylethyl) imidazolidin-2-ylidene, 1,3-di (diphenylmethyl) imidazolidin-2-ylidene, 1,3-di (1′-naphthylethyl) ) Imidazolidine-2-ylidene, 1,3-di (1′-cyclohexylethyl) imidazolidin-2-ylidene, and the like.

The anionic ligands (X ¹ and X ² ) in the compound represented by the general formula (3) are ligands having a negative charge when separated from the central metal (Ru). Any neutral electron-donating compound (L
² ) may be any ligand as long as it is a ligand having a neutral charge when separated from the central metal, that is, a Lewis base.

Such anionic ligands (X ¹ and X
² ) Specific examples of fluorine (F), bromine (Br),
Halogen atoms such as chlorine (Cl) and iodine (I), hydrogen, acetylacetone, diketonate group, substituted cyclopentadienyl group, substituted allyl group, alkenyl group, alkyl group, aryl group, alkoxy group, aryloxy group,
Examples include an alkoxycarbonyl group, a carboxyl group, an alkyl or aryl sulfonate group, an alkylthio group, an alkenylthio group, an arylthio group, an alkylsulfonyl group, and an alkylsulfinyl group.

Specific examples of the neutral ligand (L ² ) include oxygen atoms, water, carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinites, Examples include phosphites, sulfoxides, thioethers, amides, aromatic compounds, cyclic diolefins, olefins, isocyanides, thiocyanates, carbene compounds, and the like.

Specific examples of R ¹ and R ² include hydrogen, alkenyl, alkynyl, alkyl, aryl, carboxyl, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, Arylthio group, alkylsulfonyl group,
An alkylsulfinyl group can be mentioned.

Specific examples of the ruthenium compound represented by the general formula (3) include bis (1,3-diisopropylimidazolidine-2-ylidene) benzylidene ruthenium dichloride and bis (1,3-dicyclohexylimidazolidin-2). -Ylidene) benzylidene ruthenium dichloride, bis (1,3-diisopropyl-4-imidazoline-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) benzylidene ruthenium dichloride and the like. A ruthenium compound to which a heteroatom-containing carbene compound is coordinated; (1,3-dicyclohexylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride;
(1,3-Dicyclohexyl-4-imidazoline-2-
(Ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, [1,3-di (1′-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride, [1,3-di (1 '-Phenylethyl)-
4-imidazolidin-2-ylidene] (pentamethylcyclopentadienyl) benzylidene ruthenium dichloride, [1,3-di (diphenylmethyl) -4-imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (diphenylmethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (1′-cyclohexylethyl) imidazolidin-2-ylidene] ( Tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (1′-cyclohexylethyl)
[Imidazoline-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride and other ruthenium compounds in which a heteroatom-containing carbene compound and a neutral electron-donating compound are coordinated.

In the present invention, the polymerization reaction using the ruthenium compound can be carried out without a solvent, but it is preferable to carry out the polymerization in a solvent in order to carry out the hydrogenation reaction in the solvent after the polymerization. The solvent used in the present invention is not particularly limited as long as the polymer and the polymer hydride dissolve under predetermined conditions and do not affect the polymerization and the hydrogenation.

Specific examples of such a solvent include aliphatic hydrocarbon solvents such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, deca Hydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane,
Alicyclic hydrocarbon solvents such as cyclooctane; Aromatic hydrocarbon solvents such as benzene, toluene and xylene;
Nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; ether solvents such as diethyl ether and tetrahydrofuran can be used. Among them, industrially-used aromatic hydrocarbon solvents are preferable. Aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents are preferred, and are inactive during the polymerization reaction and hydrogenation reaction, and from the viewpoint of excellent polymer solubility, alicyclic solvents such as cyclohexane. Most preferably, a hydrocarbon solvent is used.

(Cyclic olefins) The cyclic olefins used in the present invention include (1) polycyclic cyclic olefins having a norbornene ring such as norbornenes, dicyclopentadienes, and tetracyclododecenes; Cyclic cyclic olefins, etc. can be used, and these cyclic olefins may have a substituent such as an alkyl group, an alkenyl group, or an alkylidene group, and may have a polar group. And a double bond other than the double bond of the norbornene ring. Among these cyclic olefins, in order to obtain a ring-opened polymer hydride having excellent heat resistance and solubility, a tricyclic compound having a norbornene ring is required.
It is preferable to use hexacyclic olefins, and particularly preferable are tricyclic olefins such as dicyclopentadiene or tetracyclic olefins such as tetracyclododecene.

[0030] The dicyclopentadiene compound dicyclopentadiene compound, refers to a cyclic olefins 3 rings having a norbornene ring, alkyl group or alkenyl group may have a substituent such as an alkylidene group. Specific examples of such dicyclopentadienes include, for example, dicyclopentadiene and methyl-dicyclopentadiene. Tricyclo [4.
3.1 ^2,5 . 0] -dec-3-ene and the like.

[0031] Tetracyclododecene such tetracyclododecene compound is represented by the following general formula (7).

[0032]

Embedded image

[0033] ^(wherein, R 19 ^{to R 26} represents a hydrogen atom, a hydrocarbon group or a halogen atom having 1 to 3 carbon ^{atoms, R 27}
To R ³⁰ is a hydrogen atom, a hydrocarbon group or a halogen atom having 1 to 20 carbon atoms, a silicon atom, a group containing an oxygen atom or a nitrogen atom, may form a ring by bonding R ²⁷ and R ^{3 0} Good. )

The tetracyclododecenes include (a) those having no double bond other than the norbornene ring, (b) those having a double bond other than the norbornene ring, (c) those having an aromatic ring, and (d) ) It can be classified into those having a polar group, etc., and any monomer can be used.

(A) Specific examples of the compound having no double bond other than the norbornene ring include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, and 8-cyclohexyltetracyclo. Examples thereof include tetracyclododecenes such as dodecene and 8-cyclopentyltetracyclododecene, and those having a substituent in the above tetracyclododecenes.

(B) Specific examples of those having a double bond other than the norbornene ring include, for example, 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, Examples thereof include tetracyclododecenes having a double bond outside the ring, such as propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, and 8-cyclopentenyltetracyclododecene.

(C) Specific examples of those having an aromatic ring include 8-phenyltetracyclododecene.

(D) Specific examples having a polar group include, for example, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, Tetracyclododecenes having a substituent containing an oxygen atom, such as carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, and tetracyclododecene-8,9-dicarboxylic anhydride; 8- Cyanotetracyclododecene, tetracyclododecene-8,9
Tetracyclododecenes having a substituent containing a nitrogen atom such as dicarboxylic imide; tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; 8-trimethoxysilyltetra Tetracyclododecene having a substituent containing a silicon atom such as cyclododecene is given.

Other cyclic ole having a norbornene ring
Fins In the present invention, in addition to the above-mentioned cyclic olefins, other cyclic olefins having a norbornene ring can also be used.

Specific examples of other cyclic olefins having a norbornene ring include bicyclic compounds having one norbornene ring, such as norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, 5
Norbornenes such as cyclopentyl norbornene;
Oxanorbornene, 5-methyloxanorbornene,
Oxanorbornenes such as 5-ethyloxanorbornene, 5-butyloxanorbornene, 5-hexyloxanorbornene, 5-decyloxanorbornene, 5-cyclohexyloxanorbornene, 5-cyclopentyloxanorbornene; 5-ethylidenenorbornene, 5-vinylnorbornene , 5-propenylnorbornene, 5-cyclohexenylnorbornene, 5-cyclopentenylnorbornene and the like having a exocyclic double bond; 5-ethylideneoxanorbornene;
Oxanorbornenes having a double bond such as 5-vinyloxanorbornene, 5-propenyloxanorbornene, 5-cyclohexenyloxanorbornene, and 5-cyclopentenyloxanorbornene are exemplified.

As one having one norbornene ring and one six-membered ring, hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-butylhexacycloheptadecene, 12-hexyl Hexacycloheptadecene, 12-
Hexacycloheptadecenes such as decylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene; 12-ethylidenehexacycloheptadecene;
Hexacycloheptadecenes such as 2-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, and 12-cyclopentenylhexacycloheptadecene are exemplified.

[0042] As those having a norbornene ring and an aromatic ring, 5-phenyl norbornene, 5-phenyl-oxa-norbornene, tetracyclo ^{[6.5.1 2,5.} 0
^{1, 6} . 0 ^8,13] trideca -3,8,10,12-
Tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [6.
6.1 ^2,5 . 0 ^1,6 . 0 ^8,13] tetradeca -
3,8,10,12-tetraene (1,4-methano-
1,4,4a, 5,10,10a-hexahydroanthracene).

Examples of those having a polar group include 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate. Nate,
Norbornenyl-2-methyloctaneate, norbornene-5,6-dicarboxylic anhydride, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5,5-di (hydroxymethyl) norbornene, 5-hydroxy -I-propylnorbornene, 5,
Norbornenes having a polar group containing an oxygen atom, such as 6-dicarboxynorbornene and 5-methoxycarbonyl-6-carboxynorbornene;

5-methoxycarbonyloxanorbornene, 5-ethoxycarbonyloxanorbornene,
Methyl-5-methoxycarbonyloxanorbornene,
5-methyl-5-ethoxycarbonyloxanorbornene, oxanorbornenyl-2-methylpropionate, oxanorbornenyl-2-methyloctanoate,
Oxanorbornene-5,6-dicarboxylic anhydride, 5
-Hydroxymethyloxanorbornene, 5,6-di (hydroxymethyl) oxanorbornene, 5,5-di (hydroxymethyl) oxanorbornene, 5-hydroxy-i-propyloxanorbornene, 5,6-dicarboxyoxanorbornene, Oxanorbornenes having a polar group containing an oxygen atom such as -methoxycarbonyl-6-carboxyoxanorbornene; norbornenes having a polar group containing a nitrogen atom such as 5-cyanonorbornene and norbornene-5,6-dicarboxylic imide; Oxanorbornenes having a polar group containing a nitrogen atom, such as 5-cyanooxanorbornene and oxanorbornene-5,6-dicarboxylic imide, are exemplified.

When these other cyclic olefins having a norbornene ring are used, it is preferable to use those having a norbornene ring and an aromatic ring from the viewpoint of heat resistance and solubility. And tetracyclododecene.
Specifically, tetrahydrofluorenes such as 4-methano-1,4,4a, 9a-tetrahydrofluorene are
It can be copolymerized with the above-mentioned cyclopentadiene or tetracyclododecene.

Monocyclic olefins Monocyclic olefins are cyclic monoolefins or cyclic diolefins having 4 to 20, preferably 4 to 10 carbon atoms. Specific examples of the cyclic monoolefin include those described in JP-A-64-66216 such as cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene and cyclooctene, and specific examples of the cyclic diolefin. Examples of the compounds include those described in JP-A-7-cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene and phenylcyclooctadiene.
258318 and the like.

These cyclic olefins can be used independently or in combination of two or more. When dicyclopentadiene or tetracyclododecene is copolymerized with a cyclic olefin copolymerizable therewith, the composition of dicyclopentadiene or tetracyclododecene is based on the total monomer weight. The amount is not particularly limited as long as it is contained in an amount of 1% by weight or more, but from the viewpoint of the heat resistance of the polymer, the amount is preferably 10 to 100% by weight, more preferably 20 to 100% by weight. preferable.

(Polymerization reaction) In the method of the present invention, the ratio of the ruthenium compound to the cyclic olefin is usually from 1: 100 to 1: 2,000, in terms of the molar ratio of (metal ruthenium in the compound: cyclic olefin). 000, preferably 1: 500 to 1: 1,000,000, more preferably 1: 1,000 to 1: 500,000. If the amount of the ruthenium compound is too large, it becomes difficult to remove the catalyst, and if the amount is too small, sufficient polymerization activity cannot be obtained. When the polymerization is performed in a solvent, the concentration of the cyclic olefin may be 1 to 3 in the solution.
It is preferably 60% by weight, more preferably 2 to 50% by weight, particularly preferably 5 to 45% by weight. Monomer concentration of 1
When the content is less than 60% by weight, the productivity is poor. When the content is more than 60% by weight, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction becomes difficult.

The polymerization reaction is started by mixing the above-mentioned cyclic olefin and a ruthenium compound. The polymerization temperature is not particularly limited, but is generally -30 ° C to 200 ° C.
° C, preferably 0 ° C to 180 ° C. The polymerization time is 1
Minutes to 100 hours.

Further, in order to adjust the molecular weight of the obtained cyclic olefin polymer, it is preferable to add an appropriate amount of a vinyl compound. The vinyl compound to be added is not particularly limited as long as it is an organic compound having a vinyl group.
Α-olefins such as butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, i-butyl vinyl ether and allyl glycidyl ether; , Allyl acetate, allyl alcohol, glycidyl methacrylate, acrylamide and the like. The amount of the vinyl compound to be added can be arbitrarily selected in the range of 0.1 to 10 mol% based on the cyclic olefin depending on the molecular weight of the polymer. Furthermore, by adding the above-mentioned vinyl compound at the end of the polymerization to release the ruthenium compound from the terminal of the polymer, the polymer can be easily moved in a solution, and the activity of the hydrogenation reaction can be improved.

The molecular weight of the polymer obtained by the above polymerization reaction is represented by a number average molecular weight (Mn) obtained by measurement (in terms of polystyrene) by gel permeation chromatography (GPC) in consideration of a change in the hydrogenation reaction. ,
Preferably it is 1,000 to 500,000, more preferably 5,000 to 200,000.

(Hydrogenation reaction) The ring-opened polymer obtained by the above polymerization reaction has a carbon-carbon double bond in the main chain. Hydrogenate the double bond. In the hydrogenation reaction, the ruthenium compound used as a catalyst for the polymerization reaction may be used as it is as a hydrogenation catalyst, or another compound may be newly added. The reaction is carried out in the presence of these catalysts.
Perform while blowing hydrogen.

When the ruthenium compound used as the polymerization catalyst is used as a hydrogenation catalyst, the hydrogenation reaction can be carried out after polymerization by supplying hydrogen without newly adding a hydrogenation catalyst. To increase the rate, a hydrogenation catalyst may be newly added. The newly added hydrogenation catalyst may be any of those generally used in hydrogenating olefin compounds, and specific examples include the following.

Examples of the homogeneous catalyst include a catalyst comprising a combination of a transition metal compound and an alkali metal compound. For example, in the notation of (transition metal compound / alkali metal compound), (cobalt acetate / triethylaluminum),
(Nickel acetylacetonate / triisobutylaluminum), (titanocene dichloride / n-butyllithium), (zirconocene dichloride / sec-butyllithium), (tetrabutoxytitanate / dimethylmagnesium) and the like. Examples of the heterogeneous catalyst include metal catalysts such as nickel, palladium, platinum, rhodium, and ruthenium; or metal-supported catalysts in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. No. For example,
In terms of (metal / carrier), (nickel / silica), (nickel / diatomaceous earth), (nickel / alumina), (palladium / carbon), (palladium / silica), (palladium / diatomaceous earth), (palladium / diatomaceous earth) Alumina) and the like.

The hydrogenation reaction is performed in an inert solvent. The solvent can be arbitrarily selected, and the same solvents as those used in the above-mentioned polymerization reaction can be used.Aromatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and ether solvents can be used. It is preferable because the solubility of the polymer hydride is excellent, and an alicyclic hydrocarbon solvent is more preferable. Among the alicyclic hydrocarbon solvents, cyclohexane and decalin are most preferred, and among the ether solvents, tetrahydrofuran and ethylene glycol dimethyl ether are most preferred. The solvent may be usually the same as the polymerization reaction solvent, and the reaction may be performed by adding a hydrogenation catalyst to the polymerization reaction solution as it is.

The conditions for the hydrogenation reaction vary depending on the type of hydrogenation catalyst used, but the hydrogenation temperature is usually from -20 ° C to -20 ° C.
250 ° C, preferably -10 to + 220 ° C, more preferably 0 to + 200 ° C, and the hydrogen pressure is usually 0.01
-10 MPa, preferably 0.05-8 MPa, more preferably 0.1-5 MPa. If the hydrogenation temperature is too low, the reaction rate is low, and if it is too high, side reactions occur. On the other hand, if the hydrogen pressure is too low, the hydrogenation rate will be slow, and if it is too high, a high pressure reactor is required.

According to the method of the present invention, the hydrogenation reaction time is 0.1 to 10 hours, and 50% or more, preferably 80% or more, of the carbon-carbon double bonds of the main chain in the polymer. Preferably 90% or more, more preferably 95% or more, particularly preferably 99% or more can be hydrogenated.

According to the method of the present invention, the hydride is obtained in the form of a solution dissolved in a solvent, so that the used hydrogenation catalyst can be easily separated and removed. Specifically, the hydrogenation catalyst in the solution after the hydrogenation reaction is centrifuged, filtered, extracted,
And can be separated and removed by adsorption or the like. In this case, when the ruthenium compound is used as it is as the hydrogenation catalyst, it is insolubilized with a metal salt or the like and then separated and removed by filtration or centrifugation, or adsorbed on an adsorbent, or in an acidic aqueous solution such as hydrochloric acid. Separation and removal by an extraction method.

[0059]

The present invention will be described more specifically below with reference to examples and comparative examples. (1) The molecular weight was measured in terms of polystyrene by GPC using tetrahydrofuran as a solvent in the case of a ring-opened polymer, and was measured in terms of polyisoprene by GPC using cyclohexane as a solvent in the case of a hydrogenated ring-opened polymer. . (2) The hydrogenation rate was measured by a ¹ H-NMR spectrum.

Example 1 In a 1-liter autoclave equipped with a stirrer, 300 ml of cyclohexane, 59.5 g (0.45 mol) of dicyclopentadiene and 10.5 g (0.056 mol) of 8-ethyltetracyclododecene were added.
l) and 1-hexene 0.1 as a chain transfer agent.
64 g were added. To this solution, 8.0 mg of [1,3-di (diphenylmethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride dissolved in 10 ml of THF.
(8.4 × 10 ⁻⁶ mol) was added. Solution at 60 ° C
, And the polymerization reaction solution was returned to room temperature, and a diatomaceous earth-supported nickel catalyst was used as a hydrogenation catalyst.
8 g were added. This solution is heated at 160 ° C. under a hydrogen pressure of 4 MPa.
For 6 hours to carry out a hydrogenation reaction. The hydrogenation rate of the obtained hydride was 99.5%, and the number average molecular weight (Mn) was 1
4,600 and the weight average molecular weight (Mw) was 32,100. The viscosity of the solution after the hydrogenation reaction did not change even after being left for one week in a closed container.

Comparative Example 1 [1,3-Di (diphenylmethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride was replaced with [1,3-bis (2,4,6) -Trimethylphenyl) imidazoline-
A polymerization reaction and a hydrogenation reaction were performed in the same manner as in Example 1 except that [2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride was used. The hydrogenation rate of the obtained hydride was 99.8%, and Mn was 12,1.
00, Mw was 28,300. The solution after the hydrogenation reaction was solidified after 1 hour in a closed vessel and lost fluidity.

Example 2 In a 1-liter autoclave equipped with a stirrer, 300 ml of cyclohexane, 59.5 g (0.45 mol) of dicyclopentadiene, and 10.5 g (0.056 mol) of 8-ethyltetracyclododecene were added.
l) was added. Further, 0.64 g of 1-hexene was added as a chain transfer agent. To this solution, [1,3-di (1′-phenylethyl) -4- dissolved in 10 ml of THF.
Imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride 6.9 m
g (8.4 × 10 ⁻⁶ mol) and add 1 g at 60 ° C.
The polymerization reaction was performed by stirring for hours. Next, 1.5 ml of ethyl vinyl ether dissolved in 20 ml of cyclohexane was added to the reaction solution, and then 150 ° C. and a hydrogen pressure of 5.
The mixture was stirred at 0 MPa for 6 hours to perform a hydrogenation reaction. The hydrogenation rate of the obtained hydride was 99.9%, and Mn was 14,20.
0 and Mw were 29,300. The viscosity of the solution after the hydrogenation reaction did not change even after being left for one week in a closed container.

Comparative Example 2 [1,3-di (1′-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride was replaced by [1,1
A polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Example 2 except that 3-bis (2,4,6-trimethylphenyl) imidazolidin-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride was used. . Hydrogenation rate is 99.8%, Mn is 19,700, M
w was 51,700. The solution after the hydrogenation reaction solidified after 1 hour in a closed vessel and lost fluidity.

[0064]

According to the present invention, a hydrogenated cyclic olefin ring-opening polymer having excellent solubility in an organic solvent can be obtained. Even if dicyclopentadiene or tetracyclododecene useful as a raw material monomer of the cyclic olefin ring-opening polymer hydride is used, the method of the present invention provides a cyclic olefin ring-opening weight having excellent solubility in general-purpose solvents such as cyclohexane. A combined hydride can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Florian Yacht Call 80798 Munich, Hil Tenspergerstrasse 4 F-term (reference) 4J032 CA68 CB01 CD01 CE03 CF01

Claims (1)

[Claims] 1. A ruthenium compound in which a compound containing a heteroatom to which a secondary or tertiary carbon is bonded and a methylene free radical is coordinated to a ruthenium atom in the presence of a solvent. A ring-opening metathesis polymerization of a cyclic olefin, and then hydrogenating at least 50% of carbon-carbon double bonds in the main chain of the ring-opening polymer to obtain a hydrogenated ring-opening polymer.